Modified drying oil-alkyd resins and process of making them



Patented ov. 14, 1950 MODIFIED DRYING OIL-ALKYD RESINS AND PROCESS OFMAKING THEM John B. Rust and William B. Canfield, Montclair,

N. J., assignors, by direct and mesne assignments, of one-half toMontclalr Research Corporation, a corporation of New Jersey, and onehalfto Ellis-Foster Company, a corporation of New Jersey No Drawing.Application October 21, 1944,

Serial No. 559,842

11 Claims.

I This invention relates to modified drying oilalkyd resins wherein themodifications are accomplished by means of beta-unsaturated monohydricalcohol esters of polycarboxylic acids.

Among the objects of the invention are: to provide a modified dryingoil-alkyd resin which is both light colored and fast drying; to make amodified drying oil-alkyd resin which is stable in a solvent but whichrapidly sets up to a hard, firm film immediately upon release of thesolvent; to produce a modified drying oil-alkyd resin which may bekettle-heated rapidly at relatively low temperatures to the necessarydegree of body, thus saving long periods of cooking at highertemperatures; to provide a modified drying oilalkydresin which air-driesto a hard, tough film; to obtain a drying oil-alkyd resin which may bebaked, with or without driers, at a relatively low temperature to lightcolored, hard, durable films; and to provide a modified drying oil-alkydresin which is compatible with nitrocellulose to give lacquer filmswhich are tough, elastic and harder than such nitrocellulose filmswithout the modified alkyd resin.

These and other objects are attained by modifying a drying oil-alkydresin with an ester containing a plurality of double bonds andcomprising a polymerizable beta-unsaturated monohydric alcohol ester ofa polycarboxylic acid. Esters of this type arehigh boiling, whichpermits the reactants to be heated without loss by volatilization, andthey react with the alkyd resin to form a light-colored resin ofimproved hardening characteristics. Examples of polycarboxylic acidesters of this type are:

A. The diesters of beta-unsaturated monohydric alcohols and saturateddibasic acids,.

acid radicals thereof combined with a polymer- I izable polycarboxylicacidester containing a plurality of double bonds.

The alkyd resin which is to be modified may be first prepared andsubsequently reacted with the unsaturated ester, or all the ingredientsof the alkyd resin (drying oil acids, polycarboxylic acid, polyhydricalcohol), together with the unsaturated ester, may be heatedsimultaneously. Various other modifications may also be used. Forexample, the polyhydric alcohol and the drying oil acids may be firstcombined and the reaction product thereof then heated with thepolycarboxylic acid and the unsaturated ester. Or, the polycarboxylicacid and the polyhydric alcohol may be at least partially combined andthis product reacted with the drying oil acids in the presence of theunsaturated ester.

A wide selection of polycarboxylic acids, polyhydric alcohols and dryingoil acids is available for the production of the drying oil alkyds usedherein. In the examples which follow the reactants have been limited tothose used in the making of the more familiar types of alkyd resins, butthey may include many others.

Among the poylhydric alcohols so included are glycerol, diethyleneglycol, pentaerythritol, dipentaerythritol, sorbitol, mannitol,trihydroxy- 'me'thylaminomethane, trimethylolpropane, and

maleic anhydride, fumaric acid, phthalic anhyrepresented by the diestersof allyl, methallyl,

crotyl, and chloroallyl alcohol and saturated acids such as phthalic,succinic, adipic, sebacic acid andof alpha-unsaturatedalpha-beta-dicarboxylic acids with conjugated polyenes as illustrated bythe butadiene-maleic adduct, cyclopentadienefumaric acid adduct,isoprene-acetylene dicarboxylic acid adduct, etc. The esters used hereinare polyfunctional, containing at least two double boncs. The modifieddrying oil-alkyd resin of this invention is one that has the drying oilfatty dride, succinic acid, malonic acid, adipic acid, sebacic acid andthe like, and various maleic acid adducts such as those fromcyclopentadiene and terpenes.

Among the fatty acids so included are those of linseed oil, cottonseedoil, China-wood oil, oiticica oil, perilla oil, soya bean oil, sunflowerseed oil, and the like. Also the individual acids and such unsaturatedacids as oleic are to be regarded in the same manner.

The following is an outline of the process when I all ingredients areheated simultaneously. A mixture containing a polyhydric alcohol, dryingoil acids, polycarboxylic acid and a beta-unsaturated monohydric alcoholester of a polycarboxylic acid, such as diallyl maleate, is heated at200-250 C. for about to 4 hours, depending upon the temperature. Asuitable reactor may be a kettle provided with thermometer,air-condenser and agitator. During heating the reaction mixture thickensrapidly and finally a stage is reached where a cold dropof the melt on aglass plate can be pulled out into strings. The period between theinitial string stage and the point of gelation is relatively short, sothat rapid cooling is sometimes necessary to prevent the formation of aninsoluble and infusible resin. Since the reaction temperature isrelatively low the cooling may often be hastened by cutting with asolvent for the resin. 4

The same general procedure of heating is used with the above-notedalternative methods of mak-- ing the products of this invention and inall cases the unsaturated ester is heated with the ingredients which go.to make up a drying oil-alkyd resin, these latter ingredients being ina previously reacted, partially reacted or unreacted form. The processresults in a light colored, tough, alkyd resin of low molecular weightand soluble in various solvents, particularly coal-tar hydrocarbons, toform quick-hardening coating compositions. The amount of solvent neededto get a solution of suitable working consistency is from 40 to about60% by weight. Solvents include aromatic hydrocarbons, esters, ketones,alcohol-ethers and higher alcohols. Aliphatic hydrocarbons may be usedas diluents.

To obtain the modified alkyd resins of this invention the unsaturatedester (e. g., diallyl maleate) is required in amount equivalent to aboutto 40% of the composition, and drying oil acids between about 40% and60%.

The compositions may be further modified in various ways with otherresins. For example, a drying oil-alkyd resin in association with aphenol-aldehyde condensation product or other resin can be treated withan unsaturated polyalcohol-modified urea-formaldehyde resin in asolution of the modified alkyd resin.

The following examples are given to illustrate the invention, and in nocase should be considered as limiting. Parts are by weight.

Example 1.-24 8 parts of glycerol, 37.8 parts of linseed oil acids, 42.8parts of phthalic anhydride, and 26.8 parts of diallyl maleate areheated together to 200 C. in 25 minutes and maintained at 200-220 C. for55 minutes. The alkyd resin was soluble, light-colored, clear, and couldbe drawn into strings 18"-24" in length.

Example 2.--31 arts of glycerol, 47.3 parts of linseed oil acids, 58.5parts of phthalic anhydride, and 16.5 parts of diallyl maleate wereheated to 200 C. over a period of 17 minutes. Heating was continued at200-220 C. for 63 minutes. A clear, light colored, soluble alkyd resinwas secured, which could be drawn into strings 18"24" long.

Example 3.-42 parts of linseed oil acids, 9.2 parts of glycerol, 11.1parts of phthalic anhydride, and 25 parts of diallyl fumarate wereheated to 210 C. over a period of 20 minutes. Heating was continued at210-230 C. for 1% hours. This produced a light-colored, clear, solublealkyd resin which could be drawn into strings 18"-21" in length.

Example 4.-18 4 parts of glycerol, 38 parts of soya bean oil acids, 29.6parts of phthalic anhydride, and 31.2 parts of monoallyl maleate wereheated together to 200 C. in 25 minutes. Heating was continuedthereafter at 210-220 C. v for approximately 1% hours. A clear,lightcolored, soluble alkyd resin was obtained which could be drawn intostrings 18"-21" long.

Example 5.80 parts of a drying oil alkyd resin known to the trade asRezyl 1103 (a phthalic glyceride drying oil acids resin containing 40% 4base phthalate resin (glyceryl phthalate) and 60% drying oil acids, andpossessing an acid number of 27-34), and 21 parts-of diallyl itaconatewere heated together to 200 C. over a period of /2 hour. Heating wascontinued at 210-230 C. for 1% hours. A light-colored, clear alkyd resinresulted which could be drawn into strings 15"-18" in length. The alkydresin was reduced to solids with xylol.

Example 6.80 parts of a drying oil modified alkyd resin commerciallyknown as Rezyl 116 (a vegetable oil acids modified polyhydricalcoholpolycarboxylic acid resin containing 75% drying oil acids and 25%phthalic glyceride) and 20 parts of diallyl maleate were heated togetherto 200 C. over a period of 40 minutes. Heating was continued at 210-230C. for 2 hours. A lightcolored, clear, soluble resin was obtained whichcould be drawn into a string 18"-21" in length,

Example 7.24.8 parts of glycerol, 37.8 parts of linseed oil acids, 42.8parts of phthalic anhydride, and 26.3 parts of diallyl phthalate wereheated together to 200 C. over a period of 25 minutes. Heating wascontinued at 210-230 C. for 1% hours. By this means a light-colored,clear, soluble alkyd resin was produced which could be drawn into astring 18"24" in length.

Example 8.37.8 parts of linseed oil acids, 24.8 parts of glycerol, 42.8parts of phthalic anhydride, and 26.3 parts of the diallyl ester ofcyclopentadiene-maleic acid were heated together to 200 C. over a periodof 40 minutes. Heating was continued at 210-220 C. for a period ofminutes. A light-colored, clear, soluble alkyd resin was secured whichcould be drawn into a string 18"-24" in length.

Example 9.24.8 parts of glycerol, 37.8 parts of linseed oil acids, and42.8 parts of phthalic anhydride, and 26.3 parts of a reaction productof diallyl fumarate and cyclopentadiene were heated together to 200 C.over a period of 25 minutes. Heating was continued for 1% hours. Theprodnot was a light-colored, clear, soluble alkyd resin which could bedrawn into strings 18"-24" in 4 length.

Example 10.36.3 parts of trihydroxymethylamino methane and 84 parts ofsoya bean oil acids were heated at 230-240 C. for 2 hours. 66.6 parts ofphthalic anhydride and 42.7 parts of the diallyl ester of abutadiene-maleic anhydride adduct (diallyl tetrahydrophthalate) werethen added and heating continued at 210-230 C. for 1% hours. Alight-colored, clear, soluble resin was obtained which could be drawninto strings 18"-24" in length.

Example 11.35 parts of linseed oil acids, 23.1 parts of glycerol, 63parts of sebacic acid and 269 parts of the diallyl ester of anisoprenemaleic anhydride adduct (diallyl methyl-tetra- 0 hydrophthalate)were heated together to 200 C; in 30 minutes. Heating was continued at210-230 C. for hours. A clear, light-colored, soluble alkyd resin wasproduced which could be drawn into strings 18"-24" long.

Example 12.-40.8 parts .of pentaerythritol, and 84.0 parts of soya beanoil acids were heated together at 230 C. for 2 hours. 66.6 parts ofphthalic anhydride and 42.7 parts of the diallyl ester of anisoprene-maleic anhydride adduct were added and heating continued at210'-230 C.

13,4 parts or glycerol were heated together at resin was clear andlight-colored, and, could be drawn into strings "-18" in length. 1 Thefollowing example is intended to show the rapidity with which the resinsof this invention are convertible by heat to the insoluble, infusibleform.

Example 14.-16.8 parts (0.06 mole) of linseed oil acids, 11.0 parts.(0.12 mole) of glycerol, 22.2

parts (0.15 'mole) of phthalic anhydride, and

part of diallyl maleate were heated together to 200 C. in V hour.Heating was continued at 200-220 C. for minutes, whereupon an insoluble,infusible resin was secured. This may be compared with an alkyd resinformed from equal moles of phthalic anhydride, glycerol and linseed oilacids, which does not gel in 4 hours when heated at 240-250 C.

(A) Baking tests.-Resin solutions (50% in xylene) of the various solubleresins given above as examples were flowed on glass plates and thenair-dried for 1 hour, followed by baking for 1 hour at 140 C. Thefollowing shows the relative hardness and color.

Sward Hard- Example ness (B) Air-drying .tests.-Resin solutionscontaining 50% solids to which were added 0.5 lead and 0.02% cobaltdrier (as naphthenates) were poured and allowed to air-dry. Thefollowing table shows the time required by each example to dry.

(C) Nitrocellulose lacquers.-Several resins of this invention wereblended with half-second nitrocellulose to form lacquers of thefollowing composition:

6.6! parts of resin a 333- parts of nitrocellulose 10.00 parts of xylol20.00 parts of butyl acetate The nitrocellulose-resin lacquer solutionswere flowed on glass plates and allowed to air-dry. The Sward Rockerhardness of these films was obtained after 1 and 24 hours to observe therate of drying.

, Sword Kalil? Example lhour 24houm Buy! 1103 31 M We claim:

1. A soluble modified drying oil-alkyd resin, a drop of which may bedrawn into strings, comprising the non-catalyzed product, at between 200and 250 C., of a polymerizable polycarboxylic acid ester containing aplurality of carbon-carbon double bonds and comprising a betaunsaturated monohydric alcohol ester of a polycarboxylic acid selectedfrom the group consisting of diesters of allyl, methallyl, crotyl, andchloroallyl alcohols with phthalic, succinic, adipic, sebacic, maleic,fumaric, citraconic, itaconic, chloromaleic, 3:6-dihydrophthalic acids,butadiene-maleic adduct, cyclopentadiene fumaric adduct andisoprene-acetylene dicarboxylic acid adduct, diesters of allyl alcoholwith cyclopentadiene-maleic adduct and isoprene-m'aleic adduct, andmonesters of allyl, methallyl, crotyl, and chloroallyl alcohols withmaleic, fumaric, citraconic, itaconic, chloromaleic, 3:6-dihydrophthalic acids, butadiene-maleic adduct, cyclopentadiene-fumaricadduct, and isoprene-acetylene dicarboxylic acid adduct, with a dryingoilalkyd resin formed by reacting the fatty acids of a drying oilselected from the group consisting of linseed, cottonseed, China-wood,oiticica, perilla, soya bean and sunflower seed oils, a polyhydricalcohol selected from the group consisting of glycerol, diethyleneglycol, pentaerythritol, di pentaerythritol, sorbitol, mannitol,trihydroxymethylamino-methane, and trimethylolpropane, and apolycarboxylic acid selected from the group .consisting of maleicanhydride, fumaric acid,

phthalic acid, adipic acid, sebacic acid, and cy clopentadiene-maleicadduct, the unsaturated ester being 10% to 40% by weight of thecomposition, the said fatty acids being from 40% to a 60% by weight ofthe composition.

2 A soluble modified drying oil-alkyd resin as set forth in claim 1 inwhich the polymerizable ester is an allyl ester of an alpha-unsaturatedalpha-beta dicarboxylic acid.

3. A soluble modified drying oil-alkyd resin a drop of which may bedrawn into strings, comprising the non-catalyzed reaction product, at

between 200 and 250 C., of an allyl ester of a 3:6-dihydrophthalic acid,with a drying oil alkyd resin formed by reacting the fatty acids of adrying oil selected from the group consisting of linseed, cottonseed,China-wood, oiticica, perilla, soya bean and sunflower seed oils, apolyhydric alcohol selected from the group consisting of glycerol,diethylene glycol, pentaerythritol, dipentaerythritol, sorbitol,mannitol, trihydroxymethylaminomethane, and' trimethylolpropane,

and a polycarboxylic acid selected from the group consisting of maleicanhydride, fumaric acid, phthalic acid, adipic acid, sebacic acid, and

cyclopentadiene-maleic adduct, the allyl ester being 10% to 40% of thecomposition, the said fatty acids being from 40% to 60% by weight of thecomposition.

4. A soluble modified drying oil-alkyd resin as set forth in claim 1 inwhich the polymerizable ester is a diallyl ester of an alpha-unsaturatedalpha-beta dicarboxylic acid.

5. A soluble modified drying oil-alkyd resin a drop of which may bedrawn into strings, comprising the non-catalyzed reaction product, atbetween 200 and 250 0., of diallyl maleate, with a drying oil-alkydresin formed by reacting the fatty acids of a drying oil selected fromthe group consisting of linseed, cottonseed, China-wood,

oiticica, perilla, soya bean and sunflower seed oils, a polyhydricalcohol selected from the group con sisting of gly erol, diethyleneglycol, pentaerythritol, dipentaerythritol, sorbitol, mannitol,trihydroxymethylaminomethane, and trimethylol-- prising thenon-catalyzed reaction product, at

between 200" and 250 C., of diallyl cyclopentadiene-maleate with adrying oil-alkyd resin formed by reacting the fatty acids of a dryingoil selected from the group consisting of linseed, cottonseed,China-wood, oiticica, perilla, soya bean and sunflower seed oils, apolyhydric alcohol selected from the group consisting of glycerol,diethylene glycol, pentaerythritol, dipentaerythritol, sorbitol,mannitol, trihydroxymethylaminomethane, and trimethylolpropane, and apolycarboxylic acid selected from the group consisting of maleicanhydride, fumaric acid, phthalic acid, adipic acid, sebacic acid andcyclopentadienemaleic adduct, the diallyl ester being 10% to of thecomposition, the said fatty acids being from 40% to 60% by weight of thecomposition.

7. A soluble modified drying oil-alkyd resin, comprising the reactionproduct, at between 200 and 250 0., of diallyl phthalate with a dryingoil-alkyd resin formed by reacting the fatty acids of a drying oil,selected from the group consisting of linseed, cotton seed, China-wood,oiticica, perilla, soya beanrand sunflower seed oils, a polyhydricalcohol selected from the group consisting of glycerol, diethyleneglycol, pentaerythritol, dipentaerythritol, sorbitol, mannitol,trihydroxymethylaminomcthane, and trimethylolpropane, and apolyc'arboxylic acid selected from the group consisting of maleicanhydride, i'umaric acid,

phthalic acid, adipic acid, sebacic acid and cyclopentadiene-maleicadduct, the diallyl phthalate being 10% to 40% of the composition, thesaid fatty acids being from 40% to 60% by weight of the composition.

8. A soluble modified drying oil-alkyd resin a drop of which may bedrawn into strings, comprising the non-catalyzed reaction product, atbetween 200 and 250 C., of a polymerizable polycarboxylic acid estercontaining a plurality of carbon-carbon double bonds and comprising abeta-unsaturated monohydric alcohol ester of a polycarboxylic acidselected from the group consisting oi. diesters of allyl, methallyl,crotyl, and chloroallyl alcohols with phthalic, succinic,

conic, chloromaleic, 3:6-dihydrophthalic' acids, butadiene-maleicadduct, cyclopentadiene-fumaric adduct and isoprene-acetylenedicarboxylic acid adduct, diestersof allyl alcohol withcyclopentadiene-maleic adduct, and isoprene-maleic adduct, andmonoesters of allyl, methallyl, crotyl and chloroallyl alcohols withmaleic, fumaric, citraconic, itaconic, chloromaleic, 3:6-dihydrophthalicacids, butadiene-maleic adduct, cyclopentadiene-fumaric adduct, andisoprene-acetylene dicarboxylic acid adduct, with a drying oil-alkydresin formed by reacting linseed oil fatty acids, a. poiyhydric alcoholselected from the group consisting of glycerol, diethylene glycol,pentaerythritol, dipentaerythritol, sorbitol, mannitol,trihydroxymethylaminomethane, and trimethylolpropane, and apolycarboxylic acid selected from the group consisting of maleicanhydride, fumaric acid, phthalic acid, adipic acid, sebacic acid andcyclopentadiene-maleic adduct, the unsaturated alcohol ester being 10%to 40% of the composition, the said fatty acids being from 40% to byweight of the composition.

9. A soluble modified drying oil-alkyd resin a drop of which may bedrawn into strings, comprising the non-catalyzed reaction product, at

between 200 and 250 0., of a polymerizable' polycarboxylic acid estercontaining a plurality of carbon-carbon double bonds and comprising abeta-unsaturated monohydric alcohol ester of a polycarboxylic acidselected from the group consisting of diesters of allyl, methallyl,crotyl, and chloroallyl alcohols with phthalic, succinic, adipic,sebacic, maleic, fumaric, citraconic, itaconic, chloromaleic,3:6-dihydrophthalic acids, butadiene-maleic adduct,cyclopentadiene-fumaric adduct and isoprene-acetylene dicarboxylic acidadduct, diesters of allyl alcohol with cyclopentadiene-maleic adduct andisoprene-maleic adduct, and monoesters of allyl, methallyl, crotyl andchloroallyl alcohols with maleic, fumaric, citraconic, itaconic,chloroallyl alcohols with maleic, fumaric, citraconic, itaconic,chloromaleic, 3:6-dihydrophthalic acids, butadienemaleic adduct,cyclopentadiene-fumaric adduct, and isoprene-acetylene dicarboxylic acidadduct, with a drying oil-alkyl resin formed by reacting soya bean oilfatty acids, 9. polyhydric alcohol selected from the group consisting ofglycerol, diethylene glycol, pentaerythritol, dipentaerythritol,sorbitol, mannitol, trihydroxymethylaminomethane, and trimethylolpropaneand a polycarboxylic acid selected from the group consisting of maleicanhydride, furnaric acid, phthalic acid, adipic acid, sebacic acid, andcyclopentadiene-maleic adduct, the unsaturated alcohol ester being 10%to 40% of the composition, the said fatty acids being from 40% to 60% byweight of the composition.

10. A soluble modified drying oil-alkyd resin a drop of which may bedrawn into strings, comprising the non-catalyzed reaction product, atbetween 200 and 250 (2., of a polymerizable polycarboxylic acid estercontaining a plurality of carbon-carbon double bonds and comprising abeta-unsaturated monohydric alcohol ester of a polycarboxylic acidselected from the group consisting of diesters of allyl, methallyl,crotyl, and chloroallyl alcohols with phthalic, succinic, adipic,sebacic, maleic, fumaric, citraconic, itaconic, chloromaleic,3:6-dihydrophthalic acids, butadiene-maleic adduct,cyclopentadiene-fumaric adduct and isoprene-acetylene dicarboxylic acidadduct, diesters of allyl alcohol with cycloadipic, sebacic, maleic,iumaric, citraconic, ita- 15 pentadiene-maleic adduct andisoprene-maleic aesaais adduct, and monoesters of allyl, methallyl,crotyl and chioroallyl alcohols, with maleic, fumaric, citraconic,itaconic, chloromaleic, 3:6-dihydrophthalic acids, butadiene-maleicadduct, cyclopentadiene-fumaric adduct, and isoprene-acetylenedicarboxylic acid adduct, and a drying oilalkyd resin formed by reactingthe unsaturated fatty acids of a drying oil selected from the groupconsisting of linseed, cottonseed, China-wood, oiticica, perilla, soyabean and sunflower seed oils, glycerol and phthalic anhydride, theunsaturated alcohol ester being to 40% of the composition, the saidfatty acids being from 40% to 60% by weight of the composition.

11. The process of making a soluble modified drying oil-alkyd resin adrop of which may be drawn into strings, which comprises heating in theabsence of a catalyst at between 200 C. and 250 C. a mixture of apolymerizable polycarboxylic acid ester containing a plurality ofcarbon-carbon double bonds and comprising a betaunsaturated monohydricalcohol ester of a polycarboxylic acid selected from the groupconsisting of diesters of allyl, methallyl, crotyl, and chloroallylalcohols with phthalic, succinic, adipic, sebacic, maleic. fumaric,citraconic, itaconic, chloromaleic, 3:6-dihydrophthalic acids,butadiene-maleic adduct, cyclopentadiene-fumaric adduct andisoprene-acetylene dicarboxylic acid adduct, diesters of allyl alcoholwith cyclopentadiene-maleic adduct and isoprene-maleic adduct, andmonoesters of allyl, methallyl, crotyl and chlorcall yl alcohols withmaleic, fumaric,

i0 citraconic, itaconic, chloromaleic, 3:6-dihydrophthalic acids,butadiene-maleic adduct, cyclopentadiene-fumaric adduct, andisoprene-acetylene dicarboxylic acid adduct and a drying oilalkyd resinformed by reacting the unsaturated fatty acids of a drying all selectedfrom the group consisting of linseed, cottonseed, China-wood. oiticica.perilia, soya bean and sunflower seed oils, a polyhydricalcohol'selected from the group consisting of glycerol, diethyleneglycol, pentaerythritol, dipentaerythritol, sorbitol, mannitol,trihydroxymethylaminomethaneaand trimethyl olpropane, and apoiycarboxylic acid selected from the group consisting of maleicanhydride, fumaric acid, phthalic acid, adipic acid, sebacic acid, andcyclopentadiene-maleic adduct, the unsaturated alcohol ester being 10%to 40% of the composition, the said fatty acids being from 40% to byweight of the composition.

JOHN B, RUST. WILLIAM B. CANFIELD.

REFERENCES CITED I The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Great am n; Oct. a, 194

1. A SOLUBLE MODIFIED DRYING OIL-ALKYD RESIN, A DROP OF WHICH MAY BE DRAWN INTO STRINGS, COMPRISING THE NON-CATALYZED PRODUCT, AT BETWEEN 200* AND 250*C., OF A POLYMERIZABLE POLYCARBOXYLIC ACID ESTER CONTAINING A PLURALITY OF CARBON-CARBON DOUBLE BONDS AND COMPRISING A BETAUNSATURATED MONOHYDRIC ALCOHOL ESTER OF A POLYCARBOXYLIC ACID SELECTED FROM THE GROUP CONSISTING OF DIESTERS OF ALLYL, METHALLYL, CROTYL, AND CHLOROALLYL ALCOHOLS WITH PHTHALIC, SUCCINIC ADIPIC, SEBACIC, MALEIC, FUMARIC, CITRACONIC, ITACONIC, CHLOROMALEIC, 3:6-DIHYDROPHTHALIC ACIDS, BUTADIENE-MALEIC ADDUCT, CYCLOPENTADIENE FUMARIC ADDUCT AND ISOPRENE-ACETYLENE DICARBOXYLIC ACID ADDUCT, DIESTERS OF ALLYL ALCOHOL WITH CYCLOPENTADIENE-MALEIC ADDUCT AND ISOPRENE-MALEIC ADDUCT, AND MONESTERS OF ALLYL, METHALLYL, CTOYL, AND CHLOROALLYL ALCOHOLS WITH MALEIC, FUMARIC, CITRACONIC, ITACONIC, CHLOROMALEIC, 3:5-DIHYROPHTHALIC ACIDS, BUTADIENE-MALEIC ADDUCT, CYCLOPENTADIENE-FUMARIC ADDUCT, AND ISOPRENE-ACETYLENE DICARBOXYLIC ACID ADDUCT, WITH A DRYING OILALKYD RESIN FORMED BY REACTING THE FATTY ACIDS OF A DRYING OIL SELECTED FROM THE GROUP CONSISTING OF LINSEED, COTTONSEED, CHINA-WOOD, OITICICA, PERILLA, SOYA BEAN AND SUNFLOWER SEED OILS, A POLYHYDRIC ALCHOHOL SELECTED FROM THE GROUP CONSISTING OF GLYCEROL, DIETHYLENE GLYCOL, PENTAERYTHRITAOL, DIPENTAERYTHRITOL, SORBITOL, MANNITOL, THRIHYDROXYMETHYLAMINO-METHANE, AND TRIMETHYLOLPROPANE, AND A POLYCARBOXYLIC ACID SELECTED FROM THE GROUP CONSISTING OF MALEIC ANHYDRIDE, FUMARIC ACID, PHTHALIC ACID, ADIPIC ACID, SEBACIC ACID, AND CYCLOPENTADIENE-MALEIC ADDUCT, THE UNSATURATED ESTER BEING 10% TO 40% BY WEIGHT OF THE COMPOSITION, THE SAID FATTY ACIDS BEING FROM 40% TO 60% BY WEIGHT OF THE COMPOSITION. 